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US3812065A - Surface-coating compositions containing n-(substituted indazolyl-n1-methyl)hexamethylenetetraamonium halides - Google Patents

Surface-coating compositions containing n-(substituted indazolyl-n1-methyl)hexamethylenetetraamonium halides Download PDF

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US3812065A
US3812065A US00303488A US30348872A US3812065A US 3812065 A US3812065 A US 3812065A US 00303488 A US00303488 A US 00303488A US 30348872 A US30348872 A US 30348872A US 3812065 A US3812065 A US 3812065A
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methyl
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hexamethylenetetraammonium
chloride
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P Minieri
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KAY-FRIES Inc
TENNECO CHEM INC US
Evonik Corp
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Tenneco Chemicals Inc
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Assigned to KAY-FRIES HOLDING INC. reassignment KAY-FRIES HOLDING INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). JUNE 10, 1988, NEW YORK Assignors: DYNAMIT NOBEL OF AMERICA INC.
Assigned to HULS AMERICA INC. reassignment HULS AMERICA INC. MERGER (SEE DOCUMENT FOR DETAILS). NOVEMBER 28, 1988. DELAWARE Assignors: DYANAMIT NOBEL CHEMICALS, INC., A CORP. OF DE., KAY-FRIES HOLDING INC., A CORP. OF NY, NKAY-FRIES, INC., A CORP. OF NY, NUODEX INC., A CORP. OF DE., PENN VINYL CORPORATION, A CORP. OF PA., PETRARCH SYSTEMS, INC., A CORP. OF PA.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • compositions contain as biocide a compound having the structural formula wherein X represents halogen, nitro, amino, acetamino, or (halobenzylidene) amino; Y represents hydrogen or halogen; Z represents halogen; and n represents an integer in the range of Zero to 2.
  • This invention relates to surface-coating compositions. More particularly, it relates to surface-coating compositions containing N-(substituted indazolyl-N -methyl)hexamethylenetetraammonium halides that have improved resistance to deterioration resulting from attack by fungi and other organisms.
  • paints and varnishes often have inadequate resistance to the action of microorganisms.
  • Some of these coating compositions such as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi.
  • Others for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and as thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full-scale utilization, particularly in those areas and in those applications that are conducive to such attack.
  • biocidal materials have been suggested for use in surface-coating compositions, but none has proven to be entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others undergo sulfide staining, and still others tend to separate from the applied coating by migration, volati1ization, or leaching once the coating has been spread in a thin layer over the surface to be protected.
  • surface-coating compositions can be protected from attack by fungi and other microorganisms by incorporating in them a new class of biocides.
  • biocides which are thoroughly compatible with the resinous binders that are commonly used in surface-coating compositions and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by fungi, bacteria, and other microorganisms without adversely affecting the viscosity and other physical properties of the surface-coating compositions.
  • biocidal compounds that are used in the surfacecoating compositions of this invention may be represented by the structural formula wherein X represents chlorine, bromine, fluorine, iodine, nitro, amino, acetamino, (chlorobenzylidene)amino, or (bromobenzylidene)amino; Y represents hydrogen, chlorine, bromine, tfiuorine, or iodine; Z represents chlorine, bromine, fluorine, or iodine; and n represents an integer in the range of zero to 2.
  • X represents chlorine, bromine, fluorine, iodine, nitro, amino, acetamino, (chlorobenzylidene)amino, or (bromobenzylidene)amino
  • Y represents hydrogen, chlorine, bromine, tfiuorine, or iodine
  • Z represents chlorine, bromine, fluorine, or iodine
  • n represents an integer in
  • biocides for use in surface-coating compositions are the compounds represented by the structural formula wherein X represents chlorine or nitro, Y represent hydrogen or chlorine, and n represents an integer in the range of zero to 2.
  • X represents chlorine or nitro
  • Y represent hydrogen or chlorine
  • n represents an integer in the range of zero to 2.
  • these preferred compounds include N-(3-chloroindazolyl-N -methyl)hexamethylenetetraammonium chloride,
  • novel compounds of this invention may be prepared by any suitable and convenient procedure.
  • they may be prepared by heating the appropriate N -halornethyl-substituted-indazole with hexamethylenetetramine.
  • the reaction is usually carried out in a solvent, such as chloroform, carbon tetrachloride, or ethylene dichloride, at the reflux temperature of the reaction mixture.
  • the N -halomethyl-substituted-indazoles may be prepared by the procedure described in my copending application Ser. No. 589,235, which was filed on Oct. 25, 1966 and which is now U.S. Pat. No. 3,637,736.
  • biocidal compounds of this invention can be used to impart fungal and bacterial resistance to a wide variety of surface-coating compositions including both solventbased and water-based coating systems. They are of particular value as biocides in surface-coating compositions that contain as their resinous binder an organic, waterinsoluble, film-forming resin that is a synthetic linear addition polymer or an oleoresinous binder.
  • novel quaternary ammonium halides are used as biocides in aqueous dispersions that contain about to 60 percent by weight of a water-insoluble linear addition polymer and/or an oleoresinous binder.
  • the aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically-unsaturated compounds, especially those of monoethylenically-unsaturated character, although butadiene, chlorobutadiene, and isoprene may be used to some extent.
  • Illustrative of the synthetic linear addition polymers that can be used as the resinous binder in the aqueous dispersions are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of styrene with maleic anhydride; and mixtures thereof.
  • Suitable oleoresinous binders include drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safiiower oil, or fish oil, bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as limed rosin, an ester gum, or phenolic resin; oleoresinous varnishes for-med by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboxylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
  • drying oils such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safiiower oil, or fish oil, bodied drying oils
  • a resin component such as limed rosin, an
  • novel compounds are used as the biocide in organic solvent-based systems that contain an oleoresinous binder as hereinbefore defined.
  • biocidal compound Only a small concentration of the biocidal compound need be present in the surface-coating compositions. As little as 0.10 percent of one or more of these compounds, based on the weight of the composition, will bring about an appreciable improvement in the resistance of the composition to attack by microorganisms. Approximately 5.0% or more of the biocidal compound, based on the weight of the composition, can be used, but these larger amounts generally do not provide further improvement in the properties of the surface-coating compositions and for this reason are not ordinarily used.
  • the amount of the biocide that will provide optimum protection for the surface-coating compositions depends upon such factors as the choice of biocidal compound, the choice of resinous binder and other components of the composition, the amount of each that is employed, and the application for which the coating composition is intended, in most cases about 0.25 percent to 2.0 percent of the biocidal compound, based on the weight of the surface-coat ing composition, is used.
  • the surface-coating compositions of this invention may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, defoaming agents, driers, emulsifying agents, dispersing agents, plasticizers, and the like in the amounts ordinarily used for these purposes.
  • the biocidal compounds may be incorporated into the surface-coating compositions by any convenient procedure. For example, they can be combined with pigments and various other components to form a pigment phase that is then mixed with the resinous binder and water or an organic solvent to form the surface-coating composition. Alternatively, they can be added to a composition that contains the resinous binder, pigment, and water or organic solvent.
  • the biocidal compound can be added as such to the other components of the surface-coating composition, or they can be added as a solution in an alcohol, ether, ketone or other solvent.
  • EXAMPLE 1 A mixture of ml. of chloroform, 11.0 grams (0.08 mole) of hexamethylenetetramine, and 16.6 grams (0.08 mole) of N'-chloromethyl-6-nitroindazole was heated at its reflux temperature for 2 hours and then cooled to 5 C. The product was isolated by filtration and then washed with cold coloroform. The combined filtrate and chloroform washings were evaporated to one-third of the original volume and then filtered. The two crops of N-(6- nitroindazolyl-N methyl)hexamethylenetetraammonium chloride were combined and dried at 60 C. under reduced pressure.
  • Each of the other N-(substituted indazolyl-N -methyl) hexamethylenetetraammonium halides disclosed herein can be used in a similar way to control the growth of microorganisms in surface-coating systems.
  • polyvinyl acetate 350 A surface-coating composition that comprises (a) a To samples of this paint was added 2 percent by weight 9 25 selectedhfrpm. the a of one of the compounds of this invention or a comparacpnslstmg o o eorqsmous m Synt we i a five biocide tron polllyrlners fibtamecl byt tihe vmg l polymecrlizat ozl of monoe yemca y-unsa urae mon mers, an mix ures An.acryhc 1 was prepared by mlxmg together thereof and (b) about 0.10 percent to 5 percent, based on e following materials.
  • Y represents hydrogen or haloy Weight of ethyl acrylate, 325% y Weight of gen
  • Z represents halogen
  • n represents an integer in methyl methacrylate, and 1.5% by weight of the range of zero to 2.
  • a surface-coating composition as set forth in claim 1 that contains 0.25 percent to 2.0 percent, based on the weight of said composition, of the biocidal compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Abstract

SURFACE-COATING COMPOSITIONS CONTAINS AS BIOCIDE A COMPOUND HAVING THE STRUCTURAL FORMULA

1-((3-Y,(X)N-1H-INDAZOLO)-CH2-)-1-AZONIA-3,5,7-TRIAZA-

ADAMANTANE Z(-)

WHEREIN X REPRESENTS HALOGEN, NITRO, AMINO, ACETAMINO, OR (HALOBENZYLIDENE)AMINO; Y REPRESENTS HYDROGEN OR HALOGEN; Z REPRESENTS HALOGEN; AND N REPRESENTS AN INTEGER IN THE RANGE OF ZERO TO 2.

Description

li i lii 3,812,065 .Fatented May 21, 1974 U.S. Cl. 260-22 R 9 Claims ABSTRACT OF THE DISCLOSURE Surface-coating compositions contain as biocide a compound having the structural formula wherein X represents halogen, nitro, amino, acetamino, or (halobenzylidene) amino; Y represents hydrogen or halogen; Z represents halogen; and n represents an integer in the range of Zero to 2.
This is a division of my copending application Ser. No. 201,178, which was filed on Nov. 22, 1971, which is now U.S. Pat. 3,730,954.
This invention relates to surface-coating compositions. More particularly, it relates to surface-coating compositions containing N-(substituted indazolyl-N -methyl)hexamethylenetetraammonium halides that have improved resistance to deterioration resulting from attack by fungi and other organisms.
It is well known in the art that paints and varnishes often have inadequate resistance to the action of microorganisms. Some of these coating compositions, such as enamels and house paints, contain as their resinous binders drying oils, oleoresinous varnishes, or alkyd resins, which are subject to attack by fungi. Others, for example, aqueous dispersions of water-insoluble synthetic linear polymers, generally contain as plasticizers and as thickeners materials that have their origin in animal or vegetable sources and that render the compositions susceptible to mildew. The resulting deterioration of the surface-coating compositions seriously hinders their full-scale utilization, particularly in those areas and in those applications that are conducive to such attack. Various biocidal materials have been suggested for use in surface-coating compositions, but none has proven to be entirely satisfactory in this application. Some do not provide the required prolonged protection against attack by microorganisms, while others undergo sulfide staining, and still others tend to separate from the applied coating by migration, volati1ization, or leaching once the coating has been spread in a thin layer over the surface to be protected.
In accordance with this invention, it has been found that surface-coating compositions can be protected from attack by fungi and other microorganisms by incorporating in them a new class of biocides. These biocides, which are thoroughly compatible with the resinous binders that are commonly used in surface-coating compositions and which are resistant to sulfide staining, provide excellent and prolonged resistance to deterioration resulting from attack by fungi, bacteria, and other microorganisms without adversely affecting the viscosity and other physical properties of the surface-coating compositions.
The biocidal compounds that are used in the surfacecoating compositions of this invention may be represented by the structural formula wherein X represents chlorine, bromine, fluorine, iodine, nitro, amino, acetamino, (chlorobenzylidene)amino, or (bromobenzylidene)amino; Y represents hydrogen, chlorine, bromine, tfiuorine, or iodine; Z represents chlorine, bromine, fluorine, or iodine; and n represents an integer in the range of zero to 2. Illustrative of these compounds are the following:
N- (3-bromoindazolyl-N -methyl hexamethylenetetraammonium bromide,
N-(G-acetaminoindazolyl-N -methyl)hexamethylenetetraammonium iodide,
N-[6-(3,4-dichlorobenzylidene)aminoindazolyl-N methyl]hexamethylenetetraammonium chloride,
N-(4-iodoindazolyl-N -methyl]hexamethylenetetraammonium iodide,
N (3 ,5 ,6-trichloroindazoly1-N -methyl )hexamethylenetetraammonium chloride,
and the like.
Particularly effective as biocides for use in surface-coating compositions are the compounds represented by the structural formula wherein X represents chlorine or nitro, Y represent hydrogen or chlorine, and n represents an integer in the range of zero to 2. Examples of these preferred compounds include N-(3-chloroindazolyl-N -methyl)hexamethylenetetraammonium chloride,
N-(5-chloroindazolyl-N -methyl)hexamethylenetetraammonium chloride,
N-(3,5-dichloroindazolyl-N -methyl)hexamethylenetetraammonium chloride N-(5,7-dichloroindazolyl-N -methyl)hexamethylenetetraammonium chloride, and
N-(3,5,7-trichloroindazolyl-N -methyl)hexamethylenetetraammonium chloride.
The novel compounds of this invention may be prepared by any suitable and convenient procedure. For example, they may be prepared by heating the appropriate N -halornethyl-substituted-indazole with hexamethylenetetramine. The reaction is usually carried out in a solvent, such as chloroform, carbon tetrachloride, or ethylene dichloride, at the reflux temperature of the reaction mixture. The N -halomethyl-substituted-indazoles may be prepared by the procedure described in my copending application Ser. No. 589,235, which was filed on Oct. 25, 1966 and which is now U.S. Pat. No. 3,637,736.
The biocidal compounds of this invention can be used to impart fungal and bacterial resistance to a wide variety of surface-coating compositions including both solventbased and water-based coating systems. They are of particular value as biocides in surface-coating compositions that contain as their resinous binder an organic, waterinsoluble, film-forming resin that is a synthetic linear addition polymer or an oleoresinous binder.
In a preferred embodiment of the invtntion the novel quaternary ammonium halides are used as biocides in aqueous dispersions that contain about to 60 percent by weight of a water-insoluble linear addition polymer and/or an oleoresinous binder. The aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically-unsaturated compounds, especially those of monoethylenically-unsaturated character, although butadiene, chlorobutadiene, and isoprene may be used to some extent. Illustrative of the synthetic linear addition polymers that can be used as the resinous binder in the aqueous dispersions are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with acrylonitrile; copolymers of vinyl chloride with vinylidene chloride; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of styrene with maleic anhydride; and mixtures thereof. Suitable oleoresinous binders include drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, safiiower oil, or fish oil, bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as limed rosin, an ester gum, or phenolic resin; oleoresinous varnishes for-med by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alkyd resins, which are resinous products resulting from the reaction of a polyhydric alcohol, such as pentaerythritol or glycerol, with a dicarboxylic acid, such as phthalic anhydride, and fatty acids; and mixtures thereof.
In another preferred embodiment of the invention, the novel compounds are used as the biocide in organic solvent-based systems that contain an oleoresinous binder as hereinbefore defined.
Only a small concentration of the biocidal compound need be present in the surface-coating compositions. As little as 0.10 percent of one or more of these compounds, based on the weight of the composition, will bring about an appreciable improvement in the resistance of the composition to attack by microorganisms. Approximately 5.0% or more of the biocidal compound, based on the weight of the composition, can be used, but these larger amounts generally do not provide further improvement in the properties of the surface-coating compositions and for this reason are not ordinarily used. While the amount of the biocide that will provide optimum protection for the surface-coating compositions depends upon such factors as the choice of biocidal compound, the choice of resinous binder and other components of the composition, the amount of each that is employed, and the application for which the coating composition is intended, in most cases about 0.25 percent to 2.0 percent of the biocidal compound, based on the weight of the surface-coat ing composition, is used.
In addition to the resinous binder and the quaternary ammonium halide, the surface-coating compositions of this invention may contain various auxiliary materials, such as pigments, extenders, solvents, dyes, defoaming agents, driers, emulsifying agents, dispersing agents, plasticizers, and the like in the amounts ordinarily used for these purposes.
The biocidal compounds may be incorporated into the surface-coating compositions by any convenient procedure. For example, they can be combined with pigments and various other components to form a pigment phase that is then mixed with the resinous binder and water or an organic solvent to form the surface-coating composition. Alternatively, they can be added to a composition that contains the resinous binder, pigment, and water or organic solvent. The biocidal compound can be added as such to the other components of the surface-coating composition, or they can be added as a solution in an alcohol, ether, ketone or other solvent.
The invention is further illustrated by the following examples.
EXAMPLE 1 A mixture of ml. of chloroform, 11.0 grams (0.08 mole) of hexamethylenetetramine, and 16.6 grams (0.08 mole) of N'-chloromethyl-6-nitroindazole was heated at its reflux temperature for 2 hours and then cooled to 5 C. The product was isolated by filtration and then washed with cold coloroform. The combined filtrate and chloroform washings were evaporated to one-third of the original volume and then filtered. The two crops of N-(6- nitroindazolyl-N methyl)hexamethylenetetraammonium chloride were combined and dried at 60 C. under reduced pressure. There was obtained an 83.3 percent yield of N- (6 nitroindazolyl N methyl)hexamethylenetetraammonium chloride, which melted at 207-209 C. and which contained 10.8 percent Cl and 26.3 percent N (calculated, 10.1 percent CI and 27.7 percent N). The structure of the compound was confirmed by its infrared spectrum.
EXAMPLE :2
A mixture of ml. of carbon tetrachloride, 7.8 grams (0.055 mole) of hexamethylenetetramine, and 13.7 grams (0.056 mole) of N -chloromethyl-3-chloro-6-nitroindaz0le was heated at its reflux temperature for 2 hours and then cooled to 5 C. The product was isolated by filtration, washed with 25 ml. of cold carbon tetrachloride, and dried at 60 C. under reduced pressure. There was obtained a 94.8 percent yield of N-(3-chloro-6-nitroindazolyl-N methyl)hexamethylenetetraammonium chloride, which melted at 188-190 C. and which contained 44.1 percent C, 4.73 percent H, 24.3 percent N, and 18.6 percent CI (calculated, 43.4 percent C, 4.65 percent H, 25.3 percent N, and 18.3 percent C1). The structure of the compound was confirmed by its infrared spectrum.
EXAMPLES 3-6 TAB LE I Yield, percent Ex. No.
3 N-(3-chloroindazolyl-N methyl)hexamethylenetetraammonium chloride.
4.;... N- (5-ch1oroindaZolyl-N methyl)hexamethylenetetraammonium chlo- 5 N-(3chlcro-5-nitroindazolyl-N -methyl)hexamethylenetetraammonium chloride.
6 N(5,6-dinitroindazolyl- N -methyl)hexamethylenetetraammonium chloride.
' Decomposes.
M.P. Analysis, percent 0.) (calculated) Compound EXAMPLE 7 (A) A polyvinyl acetate emulsion paint was prepared by mixing together the following materials:
6 Each of the other N-(substituted indazolyl-N -methyl) hexamethylenetetraammonium halides disclosed herein can be used in a similar way to control the growth of microorganisms in surface-coating systems.
Parts by weight 5 The terms and expressions which have been employed Water 80 are used as terms of description and not of limitation. Potassium pyrophosphate 3 There is no intention in the use of such terms and ex- Calcium metasilicate 135 pressions of excluding any equivalents of the features Titanium dioxide (rutile) 220 shown and described or portions thereof, but it is recog- Aqueous solution of methylcellulose (2%) 200 10 nized that various modifications are possible within the Diethyl ether of diethylene glycol 37 scope of the invention claimed. Aqueous dispersion containing 55% by weight of What is claimed is:
polyvinyl acetate 350 1. A surface-coating composition that comprises (a) a To samples of this paint was added 2 percent by weight 9 25 selectedhfrpm. the a of one of the compounds of this invention or a comparacpnslstmg o o eorqsmous m Synt we i a five biocide tron polllyrlners fibtamecl byt tihe vmg l polymecrlizat ozl of monoe yemca y-unsa urae mon mers, an mix ures An.acryhc 1 was prepared by mlxmg together thereof and (b) about 0.10 percent to 5 percent, based on e following materials. th h f f l d Parts by Weight e we1g t o sa1 compos1 ion, 0 a 1061 a compoun Titanium dioxide 11360 20 having the structural formula Mica (325 mesh waterground) 136.0 Calcium carbonate 568.0 Water 699.0 0 Y 2% aqueous solution of sodium salt of maleic Xn on N anhydride/diisobutylene copolymer (Tamol N a 731 410 \N/ I z Alkyl aryl polyether surfactant (Triton CF-lO) 9.0 Antifoam agent (Colloid (581B) 18.0 Ethylene glycol 91.0 Hydroxyethyl cellulose '(Cellosize QP 4400) 9.1 Antifoam agent (Colloid 581B) 91.0 Aqueous dispersion containing 43% y Weight wherein X represents halogen, nitro, amino, acetamino, or
of the ammonium Salt of a copolymer of (halobenzylidene)amino; Y represents hydrogen or haloy Weight of ethyl acrylate, 325% y Weight of gen; Z represents halogen; and n represents an integer in methyl methacrylate, and 1.5% by weight of the range of zero to 2. acrylic acid containing 3% y Wbigbt 0f tert- 2. A surface-coating composition as set forth in claim ylphenoxypolyethoxyethanol 2486.0 1 wherein the biocidal compound has a structural formula To samples of this paint was added 2 percent by weight 4 of either one of the compounds of this invention or a comparative biocide.
(C) The polyvinyl acetate and acrylic paints were I evaluated by means of an agar diffusion assay. In this test agar is inoculated with the test organism, the treated 45 Q, C
1- paint is placed 1n a well out from the agar, and after 1 CH incubation at 28 C. and 85-95% relative humidity, the 2- 2' activity of the biocide is measured by zones of inhibition. CH? The biocidal compounds tested and the results obtained CHzN are given in Table II. In this table: ZO=Zone of inhibition in millimeters T =Trace zone wherein X represents chlorine or nitro; Y represents hy- .=Not tested drogen or chlorine; and n represents an integer in the range Bacteria A-Mixed inoculum consisting of P. aeruginosa of Zero o 2- ATCC 10145, A. aerogenes ATCC 7256, and three 3. A surface-coating composition as set forth in claim unidentified strains of Bacillus 2 wherein the biocidal compound is N-(6-nitroindazolyl- BBacillus subtilis N -methyl)hexamethylenetetraammonium chloride. C-Aerobacter aerogenles 4. A surface-coating composition as set forth in claim DPseudom0nas aeruginosa 2 wherein the biocidal compound is N-(3-chloroindazolyl- Fungi EPullularia pullulans 0 N -methyl)hexamethylenetetraammonium chloride. F-Penicillium crustosum 5. A surface-coating composition as set forth in claim G-Aspergillus niger 2 wherein the biocidal compound is N-(3-chloro-5-nitro- TABLE II Effect on paint Bacteria Fungi Biocide Paint pH Color A B O D E F G 7.2 6.3 8.2 6.6 7.1 6.4 as 7.0 c fiiiilii ii iiiiiiil g indazolyl-N -methyl)hexarnethylenetetraammonium chloride.
6. A surface-coating composition as set forth in claim 2 wherein the biocidal compound is N-(5,6 dinitroindazo1y1-N -methy1)hexarnethylenetetraammonium chloride.
7. A surface-coating composition as set forth in claim 1 that contains 0.25 percent to 2.0 percent, based on the weight of said composition, of the biocidal compound.
8. A surface-coating composition as set forth in claim 1 wherein the resinous binder is polyvinyl acetate.
9. A surface-coating composition as set forth in claim 1 wherein the resinous binder is a polymer of esters of acrylic acids.
References Cited DONALD E. CZAJ A, Primary Examiner 10 R. A. WHITE, Assistant Examiner US Cl. X.R.
106 -1S AF; 26029.6 MN, 45.8 NT
US00303488A 1971-11-22 1972-11-03 Surface-coating compositions containing n-(substituted indazolyl-n1-methyl)hexamethylenetetraamonium halides Expired - Lifetime US3812065A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998785A (en) * 1974-06-13 1976-12-21 International Business Machines Corporation Anti-fungal and/or anti-bacterial hardware for ink printing apparatus
FR2327277A1 (en) * 1975-10-09 1977-05-06 Hoechst Ag USE OF AZA-ADAMANTANE DERIVATIVES TO STABILIZE POLYMERIC MATERIALS

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998785A (en) * 1974-06-13 1976-12-21 International Business Machines Corporation Anti-fungal and/or anti-bacterial hardware for ink printing apparatus
FR2327277A1 (en) * 1975-10-09 1977-05-06 Hoechst Ag USE OF AZA-ADAMANTANE DERIVATIVES TO STABILIZE POLYMERIC MATERIALS
US4082723A (en) * 1975-10-09 1978-04-04 Hoechst Aktiengesellschaft Aza-adamantane compound stabilizers for organic polymer compositions

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